Internal rotation analysis of the microwave and millimeter wave spectra of fluoral (CF3CHO)

C. Bermudez*, R. A. Motiyenko, C. Cabezas, V. V. Ilyushin, L. Margulès, Y. Endo, J. C. Guillemin

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

The rotational spectrum (4–40 GHz and 50–330 GHz) has been measured and analyzed for trifluoroacetaldehyde, also known as fluoral (CF3CHO), which is one of the degradation products of the fluorinated contaminants emitted into the atmosphere. The complexity of the spectroscopic analysis of this molecule arises from the strong coupling between the internal rotation motion of CF3 group and the overall rotation of the molecule. The value obtained for its coupling constant (ρ = 0.91723481(49)) is comparable to the corresponding value of methanol (CH3OH, ρ = 0.81), which is known for its complex spectrum. A total of 12,322 transitions of the ground, the first and second excited torsional states (ΔE1υt = 62.0183(13)cm−1; ΔE2υt = 120.3315(13)cm−1) with J ≤ 50 were included in the analysis that was performed employing the rho-axis-method (RAM), and the RAM36 code. A fit within experimental error (root mean square deviation equals to 35 kHz) has been achieved for this dataset using 47 parameters of the RAM torsion-rotation Hamiltonian. In the course of the analysis, it became evident that for such high ρ value, as it is determined for fluoral, a larger than usual torsional basis set at the first diagonalization step of the two-step diagonalization procedure is required for achieving a fit within experimental error.

Original languageEnglish
Article number121071
JournalSpectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
Volume274
DOIs
StatePublished - 5 Jun 2022

Keywords

  • Atmospheric
  • Fluorinated aldehydes
  • High resolution
  • Large amplitude motion
  • Molecular spectroscopy
  • Rotational spectroscopy

Fingerprint

Dive into the research topics of 'Internal rotation analysis of the microwave and millimeter wave spectra of fluoral (CF3CHO)'. Together they form a unique fingerprint.

Cite this